EP3083553B1 - Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores - Google Patents

Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores Download PDF

Info

Publication number
EP3083553B1
EP3083553B1 EP14811922.5A EP14811922A EP3083553B1 EP 3083553 B1 EP3083553 B1 EP 3083553B1 EP 14811922 A EP14811922 A EP 14811922A EP 3083553 B1 EP3083553 B1 EP 3083553B1
Authority
EP
European Patent Office
Prior art keywords
acid
formula
group
compound
ore
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14811922.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3083553A1 (en
Inventor
Natalija Smolko-Schvarzmayr
Anders Klingberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nouryon Chemicals International BV
Original Assignee
Akzo Nobel Chemicals International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Chemicals International BV filed Critical Akzo Nobel Chemicals International BV
Priority to EP14811922.5A priority Critical patent/EP3083553B1/en
Priority to NO14811922A priority patent/NO3083553T3/no
Publication of EP3083553A1 publication Critical patent/EP3083553A1/en
Application granted granted Critical
Publication of EP3083553B1 publication Critical patent/EP3083553B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/06—Oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B03D1/011—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/016—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B03D1/021—Froth-flotation processes for treatment of phosphate ores
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/26—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one amino group bound to the carbon skeleton, e.g. lysine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/06—Depressants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores
    • B03D2203/06—Phosphate ores

Definitions

  • the present invention relates to new polyester polyquaternary ammonium compounds which can be used in a variety of applications, e.g. as corrosion inhibitors, textile conditioners, ingredients in products of personal care, and as collectors for mineral processing.
  • the new compound is obtainable by reacting alkanolamines with a mixture of polyalcohols, monocarboxylic acids and dicarboxylic acids followed by quaternising the resulting esters in a known manner.
  • polyester polyquaternary ammonium compounds became very attractive for a variety of applications due to their good performance and excellent environmental characteristics.
  • EP 0 980 352 B1 relates to compounds obtained by the reaction of triethanolamine with fatty acids and dicarboxylic acids, and/or the corresponding quaternised compounds thereof, and also to textile-softening compositions containing these compounds.
  • EP 1 136 471 A1 relates to products based on the esterification of alkanolamines, optionally alkoxylated, dicarboxylic acids and fatty alcohols, optionally alkoxylated, and esterquats obtainable therefrom.
  • the products are usable in treatments for softening and conditioning of textiles, paper and hair.
  • EP 0 770 595 A1 relates to esterquats obtained by reacting trialkanolamine with a mixture of fatty acids, dicarboxylic acids and sorbitol, optionally ethoxylating the ester, and quaternising the product. These esterquats are used in the preparation of surface active agents, especially for hair and personal care.
  • WO 2011/147855 describes the process of floating calcium carbonate containing silicates as impurity, using as collectors ester quaternary compounds, which are obtainable by the condensation of a fatty alcohol, optionally alkoxylated, a fatty acid alkanolamide, optionally alkoxylated, or an alkoxylated secondary amine, a dicarboxylic acid or a derivative thereof and an alkanolamine, where the condensation product has been quaternised by a suitable alkylating agent.
  • EP 1 949 963 B1 relates to the flotation of non-sulfidic minerals and ores where polymeric esterquats, obtained by reacting alkanolamines, fatty acids and dicarboxylic acids and quaternising the resulting esters, are used as collectors.
  • polyester polyquaternary ammonium compounds which are based on renewable raw materials and which are easily manufactured, and where said compounds have improved properties in a number of applications. It was surprisingly found that a polyester polyquaternary ammonium compound obtainable by a process including the followings steps:
  • the reverse froth flotation process comprises the use of the above-mentioned polyester polyquaternary ammonium compounds, obtainable by the condensation of a polyol having 3-4 hydroxyl groups, preferably glycerol, a dicarboxylic acid or a derivative thereof, a fatty acid, and an alkanolamine, and where the condensation product has been quaternised by a suitable alkylating agent.
  • Figure 1 is the SEC chromatogram from Example 1.
  • a first aspect of the invention relates to specific polymers obtainable from the condensation of at least one polyol having 3-4 hydroxyl groups, preferably glycerol, optionally alkoxylated, and at least one alkanolamine, optionally alkoxylated, with at least one dicarboxylic acid and at least one fatty acid, followed by quaternisation of the product obtained by the condensation, and in a second aspect the present invention relates to a method for obtaining these polymers.
  • a third aspect of the present invention relates to the use of the aforementioned products as flotation collectors, especially for the reverse froth flotation of non-sulfidic ores containing silicates as impurities, such as ores containing calcite, phosphate or ferruginous minerals, and in particular for the reverse froth flotation of apatite.
  • a fourth aspect relates to a method for the reverse froth flotation of apatite in the presence of these products.
  • polyester polyquaternary ammonium compound containing a polyol having 3-4 hydroxyl groups as a building block according to the present invention is a new compound.
  • the polyol is a compound of formula (I), where Y is -O(CH 2 CH(CH 3 )O) m1 (CH 2 CH 2 O) o (CH 2 CH(CH 3 )O) m2 T, X is H, T is H, and V and Z are both -(CH 2 CH(CH 3 )O) m1 (CH 2 CH 2 O) o (CH 2 CH(CH 3 )O) m2 T.
  • This polyol is glycerol or alkoxylated glycerol.
  • the values of m1, m2 and o are the same as above, and preferably they are all 0.
  • the average value of k and m will depend on the molar ratios of the appropriate compounds (I), (IIa) or (IIb), (III) and (IV) in the reaction mixture, as well as on the reaction conditions, the m values suitably ranging between 1 and 3, and the k values suitably ranging between 2 and 7.
  • the formula above shows one block containing esterified glycerol and diacid, and one block containing esterified alkanolamine and diacid.
  • the "block units" consisting of one glycerol esterified with one diacid may of course be distributed randomly with the "block units” consisting of one alkanolamine esterified with one diacid.
  • the fatty acids either have been esterfied with a primary OH group of a glycerol unit or of an alkanolamine unit, and thus appear at the end of the chains, or have been esterified with a secondary hydroxyl group of one or several of the glycerol units.
  • a suitable method for the preparation of the polyester polyquaternary ammonium compounds subject of the present invention comprises the steps of mixing a compound of formula (I) as defined above with a compound of formula (IIa) or (IIb) as defined above, a compound of formula (III) as defined above, and a part of a compound of formula (IV), effecting an esterification condensation reaction between the compounds in the mixture, adding the rest of compound of formula (IV) and go on esterifying the product in the reaction mixture, adding an alkylating agent to the condensation reaction product and effecting a quaternisation reaction of the condensation product.
  • esterification condensation reactions taking place between the compounds (I), (IIa) or (IIb), (III) and (IV) are well-known per se in the art.
  • the reactions may be performed with an esterification catalyst, such as a Brönstedt or Lewis acid, for example methanesulfonic acid, p-toluenesulfonic acid, citric acid or BF 3 , or without any catalyst.
  • an esterification catalyst such as a Brönstedt or Lewis acid, for example methanesulfonic acid, p-toluenesulfonic acid, citric acid or BF 3 , or without any catalyst.
  • a dicarboxylic acid derivative of formula (IIa) wherein D is O-R 4
  • the reaction is a transesterification, which alternatively could be performed in the presence of an alkaline catalyst.
  • esterification could be performed in more than one step, e.g. by first condensing the dicarboxylic acid derivative (IIa) or (IIb) with the alkanolamine (III), and then adding the compound (I) in a next step, followed by addition of (IV).
  • the reactions could take place with or without solvents added. If solvents are present during the reaction, the solvents should be inert to esterification, e.g. toluene or xylene.
  • the esterification condensation reaction between the components (I), (IIa) or (IIb), (III) and (IV) is suitably effected by heating the mixture at a temperature suitably between 120 and 220°C for a period of from 2 to 20 hours, optionally at a reduced pressure of from 0.5 to 20 KPa.
  • the molar ratio between the compound of structure (I) and the dicarboxylic acid or derivative (IIa) or (IIb) in the reaction mixture is suitably 1:1.2 to 1:10, more preferably 1:1.5 to 1:5, still more preferably 1:2 to 1:4 and most preferably 1:2 to 1:3, the ratio between the compound of structure (I) and alkanolamine (III) is suitably 1:1 to 1:8, more preferably 1:1.2 to 1:6, still more preferably 1:1.5 to 1:5, still more preferably 1:1.5 to 1:4, still more preferably 1:1.5 to 1:3 and most preferably 1:1.5 to 1:2.5, and the ratio between the compound (IV) and the dicarboxylic acid or derivative (IIa) or (IIb) is preferably 1:1 to 1:5, more preferably 1:1.5 to 1:3 and most preferably 1:1.5 to 1:2.
  • Suitable polyols having 3-4 hydroxyl groups include pentaerythritol, glycerol, trimethylolpropan
  • Compound (I) and (III) may independently be alkoxylated.
  • the alkoxylation reactions are well-known per se in the art. Generally, for the products of the present invention the following applies. If more than one type of alkylene oxide is reacted with the polyol and/or alkanolamine, the different alkylene oxides may be added in blocks in either order, or may be added randomly.
  • the alkoxylation may be performed by any suitable method known in the art by using e.g. an alkaline catalyst, such as KOH, or an acid catalyst.
  • the dicarboxylic acid derivative of general formula (IIa) or (IIb) could be a dicarboxylic acid as such, a dicarboxylic acid chloride, a diester of a dicarboxylic acid, or a cyclic anhydride of a dicarboxylic acid.
  • the most suitable derivatives are the dicarboxylic acids and their corresponding cyclic anhydrides.
  • dicarboxylic acid derivatives include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, malic acid, tartaric acid, their corresponding acid chlorides, their corresponding methyl or ethyl esters, and their corresponding cyclic anhydrides.
  • the hydrocarbyl group of the fatty acid having formula (IV) may be linear or branched, saturated or unsaturated. When substituted, the substituents are normally one or more hydroxyl groups.
  • the fatty acid may suitably be tall oil fatty acid, coco fatty acid, tallow fatty acid, soya fatty acid, rape seed fatty acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, ⁇ -linolenic acid, arachidonic acid, erucic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and mixtures thereof.
  • An example of a fatty acid that is substituted is ricinoleic acid, which is substituted by a hydroxyl group in the 12 position. The most preferred fatty acids are unsaturated.
  • Suitable alkanolamines are N-methyl diethanolamine and N-methyl diisopropanolamine, optionally alkoxylated with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. If more than one alkylene oxide is reacted with the alkanolamine, the different alkylene oxides may be added in blocks in either order, or may be added randomly.
  • quaternisation is a reaction type that is well-known in the art.
  • the alkylating agents are suitably selected from the group consisting of methyl chloride, methyl bromide, dimethyl sulphate, diethyl sulphate, dimethyl carbonate and benzyl chloride, the preferred alkylating agents being methyl chloride, dimethyl sulphate, dimethyl carbonate or benzyl chloride, and the most preferred methyl chloride.
  • the quaternisation of the alkanolamine could be performed as a first step, which would then be followed by an esterification reaction between (I), (IIa) or (IIb), (IV) and quaternised (III).
  • the quaternisation reaction is normally performed in water or a solvent, such as isopropanol (IPA) or ethanol, or in mixtures thereof, the most preferred solvent being IPA.
  • the reaction temperature of the quaternising reaction is suitably in the range of from 20 to 100°C, preferably at least 40, more preferably at least 50 and most preferably at least 55°C, and preferably at most 90°C.
  • the heating is preferably stopped when the amount of basic nitrogen is ⁇ 0.1 mmol/g, as measured by titration with 0.1 M perchloric acid in glacial acetic acid.
  • the invention relates to a method for reverse froth flotation for non-sulfidic ores containing silicate as impurities, especially phosphate ores for the recovery of apatite minerals, in which method the compound or composition described above is used as a collector.
  • non-sulfidic ore means ores where the value mineral is not in the form of a sulphide, and includes any ore that is conventionally classified as non-sulfidic, inter alia barite, calamine, calcite, magnesite, cassiterite, coal, feldspar, fluorite, glass sand, graphite, heavy metal oxides, iron ores, kaolin clay, phosphate, potash, pyrochlore, scheelite and talc.
  • the effective amount of the collector of the present invention will depend on the amount of impurities present in the pulped phosphate ore and on the desired separation effect, but will in general be in the range of from 100 to 2000 g/ton dry ore, preferably in the range of from 200 to 1500.
  • the present invention relates to a pulp comprising crushed and ground phosphate ore, a mineral collector reagent as defined herein, and optionally a depressant and further flotation aids.
  • Suitable depressants may be e.g. phosphoric acid, a polysaccharide, alkalized starch, or dextrin.
  • flotation aids that may be present in the froth flotation method are extender oils, and frothers/froth regulators, such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates.
  • frothers/froth regulators such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates.
  • Quaternisation 225 g of polyester polyamine and 106 g of isopropanol were added to the autoclave and the reaction mixture was heated up to 60°C. Then 19.6 g of methylchloride was added to the reaction mixture. The postreaction was carried out at 75°C for 17h. The total amount of basic nitrogen in the final product was 0.060 meq/g.
  • the peak at 39.5 minutes is the solvent peak and was therefore not collected for analysis.
  • a phosphate ore of sedimentary origin containing 69% of apatite, 9% of silicates (quartz and feldspar), 21 % of calcite and 1 % of dolomite was used.
  • Flotation tests were performed in a laboratory batch flotation machine with 1.5 l cell. 0.266 kg ore sample was added to the cell, tap water (Stenungsund municipal water with hardness 4°dH) was added to 1.4 l volume, and agitation with 1000 rpm was used throughout the tests. The tests were performed at a pH of 7.8-8.0 (natural) and at ambient temperature, which was 21°C.
  • the froth products and the remaining cell product were dried, weighed and analyzed for content of silicate minerals, defined as insoluble in 25% hydrochloric acid.
  • the content of acid insoluble remaining in the cell product was then calculated after first, second and third flotation step.
  • the selectivity factor is defined as the ratio between distribution of "acid insoluble” and distribution of phosphate in the froth (waste). This should be as high as possible.
  • Example 1 The collector synthesized in Example 1 was used in the flotation procedure described above, and the flotation results are displayed in Table 1. One can see from the results, that the new collector provides a high selectivity in the reverse flotation of phosphate containing ores.
  • Table 1 Total dosage of collector (g/t) Acid insoluble remaining in cell (%) Acid insoluble in froth (%) Phosphate recovery (%) Selectivity factor 700 6.02 83.93 99.32 52.81 900 2.54 83.63 98.58 52.22 1100 1.52 47.79 97.43 32.94
  • Table 1 The values in Table 1 are weight percentages.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP14811922.5A 2013-12-18 2014-12-15 Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores Active EP3083553B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP14811922.5A EP3083553B1 (en) 2013-12-18 2014-12-15 Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores
NO14811922A NO3083553T3 (https=) 2013-12-18 2014-12-15

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP13198086 2013-12-18
EP13198074 2013-12-18
EP14811922.5A EP3083553B1 (en) 2013-12-18 2014-12-15 Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores
PCT/EP2014/077669 WO2015091308A1 (en) 2013-12-18 2014-12-15 Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores

Publications (2)

Publication Number Publication Date
EP3083553A1 EP3083553A1 (en) 2016-10-26
EP3083553B1 true EP3083553B1 (en) 2017-10-18

Family

ID=52023533

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14811922.5A Active EP3083553B1 (en) 2013-12-18 2014-12-15 Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores

Country Status (11)

Country Link
US (1) US10100146B2 (https=)
EP (1) EP3083553B1 (https=)
KR (1) KR102343677B1 (https=)
BR (1) BR112016013120B1 (https=)
CA (1) CA2932866C (https=)
EA (1) EA031803B1 (https=)
ES (1) ES2651856T3 (https=)
NO (1) NO3083553T3 (https=)
SA (1) SA516371322B1 (https=)
UA (1) UA119757C2 (https=)
WO (1) WO2015091308A1 (https=)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017097816A1 (en) * 2015-12-08 2017-06-15 Clariant International Ltd Oligoester ammonium salts and their use in compositions for conditioning hair
FR3047674B1 (fr) * 2016-02-16 2018-02-16 Arkema France Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai
FR3047675B1 (fr) * 2016-02-16 2018-02-16 Arkema France Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai
EP3444036A1 (en) * 2017-08-16 2019-02-20 Omya International AG Indirect flotation process for manufacturing white pigment containing products
EP3740319B1 (de) * 2018-01-16 2024-04-03 Clariant International Ltd Esterquats zur flotation von nicht-sulfidischen mineralien und erzen und verfahren
WO2020007773A1 (en) 2018-07-03 2020-01-09 Nouryon Chemicals International B.V. Collector composition containing biodegradable compound and process for treating siliceous ores
CN113692318B (zh) * 2019-04-19 2023-06-06 诺力昂化学品国际有限公司 包含n-酰化氨基酸的捕集剂组合物和处理非硫化矿的方法
CN111036415B (zh) * 2019-11-28 2021-11-16 东北大学 一种抑制剂hedp在菱镁矿正浮选脱钙中的应用
CN111036416B (zh) * 2019-11-28 2021-11-16 东北大学 一种高效抑制剂5′-ATP-2Na在菱镁矿正浮选脱钙中的应用
WO2022243367A1 (en) 2021-05-18 2022-11-24 Nouryon Chemicals International B.V. Polyester polyquats in cleaning applications

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19539876C1 (de) 1995-10-26 1996-12-05 Henkel Kgaa Sorbitolesterquats
ES2130993B1 (es) 1997-04-30 2000-03-01 Kao Corp Sa Nueva materia activa suavizante para textiles, procedimiento para su obtencion y composiciones suavizantes para textiles que la contienen.
ES2180372B1 (es) 2000-03-22 2003-10-16 Kao Corp Sa Esteres derivados de alcanolaminas, acidos dicarboxilicos y alcoholes grasos, y los tensioactivos cationicos obtenibles a partir de los mismos.
US6562780B2 (en) * 2001-06-07 2003-05-13 Kao Corporation Esters derived from alkanolamines, dicarboxylic acids and fatty alcohols and the cationic surfactants obtainable therefrom
GB0607500D0 (en) * 2006-04-13 2006-05-24 Ici Plc Structurants for oil phases
DE602007009632D1 (de) * 2007-01-26 2010-11-18 Cognis Ip Man Gmbh Verfahren für die Flotation nichtsulfidischer Mineralien und Erze
WO2011147855A2 (en) 2010-05-28 2011-12-01 Akzo Nobel Chemicals International B.V. Quaternary ammonium compounds and their use as collectors in froth flotation processes
DE102010017635A1 (de) 2010-06-29 2011-12-29 G+R Technology Group Ag Recyclingsystem und Verfahren zum Betreiben eines Recyclingsystems
WO2012028542A1 (en) 2010-08-30 2012-03-08 Akzo Nobel Chemicals International B.V. Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors
BR112013015812B1 (pt) 2010-12-28 2020-03-24 Akzo Nobel Chemicals International B.V. Uso de um produto obtenível pela reação de um ácido graxo ou mistura de ácidos, produto obtenível pela reação de um ácido graxo ou mistura de ácidos, método para a produção de um produto e método para a proteção de uma superfície metálica contra a corrosão

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EA201691195A1 (ru) 2016-10-31
US20160304663A1 (en) 2016-10-20
ES2651856T3 (es) 2018-01-30
KR20160098286A (ko) 2016-08-18
CA2932866C (en) 2023-03-07
EA031803B1 (ru) 2019-02-28
US10100146B2 (en) 2018-10-16
NO3083553T3 (https=) 2018-03-17
BR112016013120B1 (pt) 2020-12-29
WO2015091308A1 (en) 2015-06-25
CA2932866A1 (en) 2015-06-25
KR102343677B1 (ko) 2021-12-27
EP3083553A1 (en) 2016-10-26
SA516371322B1 (ar) 2019-05-06
UA119757C2 (uk) 2019-08-12

Similar Documents

Publication Publication Date Title
EP3083553B1 (en) Polyester polyquaternary ammonium compound collectors for reverse froth flotation of silicates from nonsulfidic ores
EP2576072B1 (en) Use of quaternary ammonium compounds as collectors in froth flotation processes
US10543493B2 (en) Synthesis of new anionic surfactants and their use as collectors in froth flotation of non-sulphidic ores
EP2249967B1 (en) Oxidized and maleated derivative composition
US20050250914A1 (en) Method for the production of hyperbranched water-soluble polyesters
US11648569B2 (en) Use of alkoxylated amines as collector agents for ore beneficiation
US11802179B2 (en) Polyesteramines and polyesterquats
US10744517B2 (en) Use of alkoxylated amines as collector agents for ore beneficiation
US12180341B2 (en) Collectors for flotation process
EP0031310B1 (en) Nonionic surface active monoester and method for its production
US20210121894A1 (en) Collector composition containing biodegradable compound and process for treating siliceous ores

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160621

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20170526

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 937799

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171115

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014016103

Country of ref document: DE

Ref country code: CH

Ref legal event code: NV

Representative=s name: KASCHE AND PARTNER AG, CH

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2651856

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20180130

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20171018

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20171018

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180118

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180218

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20180400106

Country of ref document: GR

Effective date: 20180518

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014016103

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

26N No opposition filed

Effective date: 20180719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171215

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171215

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20141215

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20191227

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20191230

Year of fee payment: 6

Ref country code: FR

Payment date: 20191226

Year of fee payment: 6

Ref country code: IT

Payment date: 20191219

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20191120

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20200102

Year of fee payment: 6

Ref country code: ES

Payment date: 20200102

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20191231

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171018

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 937799

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171018

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 937799

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201215

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201215

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210707

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201216

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201215

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201216

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20241226

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20251231

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20251229

Year of fee payment: 12